CN1197819A - Thermosetting resin composition - Google Patents
Thermosetting resin composition Download PDFInfo
- Publication number
- CN1197819A CN1197819A CN98108759A CN98108759A CN1197819A CN 1197819 A CN1197819 A CN 1197819A CN 98108759 A CN98108759 A CN 98108759A CN 98108759 A CN98108759 A CN 98108759A CN 1197819 A CN1197819 A CN 1197819A
- Authority
- CN
- China
- Prior art keywords
- structural unit
- diamines
- polyimide
- polycarbodiimide
- thermosetting resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 13
- 239000011342 resin composition Substances 0.000 title abstract description 5
- 239000004642 Polyimide Substances 0.000 claims abstract description 38
- 229920001721 polyimide Polymers 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 150000004985 diamines Chemical group 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Chemical group 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 125000006159 dianhydride group Chemical group 0.000 claims description 3
- 239000002966 varnish Substances 0.000 description 23
- -1 siloxane backbone Chemical group 0.000 description 20
- 150000008064 anhydrides Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 7
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FCSSPCOFDUKHPV-UHFFFAOYSA-N 2-Propenyl propyl disulfide Chemical compound CCCSSCC=C FCSSPCOFDUKHPV-UHFFFAOYSA-N 0.000 description 3
- ZSEADYMLKBVVTB-UHFFFAOYSA-N 3-[methyl(trimethylsilyloxy)silyl]propan-1-amine Chemical class C[SiH](CCCN)O[Si](C)(C)C ZSEADYMLKBVVTB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WLGXLJGGAGAIDP-UHFFFAOYSA-N CN(C)C.[SiH3]Cl Chemical compound CN(C)C.[SiH3]Cl WLGXLJGGAGAIDP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- LRYZJEXQHWCLJY-UHFFFAOYSA-N 1-phenyl-2-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C1=CC=CC=C1 LRYZJEXQHWCLJY-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- ANEQGVKJIBRYFF-UHFFFAOYSA-N 3-ethyloxetane-2,4-dione Chemical class CCC1C(=O)OC1=O ANEQGVKJIBRYFF-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DCNKXMWSUJCATR-UHFFFAOYSA-N C1=CC=CC=C1.CC1(CC(C(=O)O)=CC=C1)C(=O)O Chemical compound C1=CC=CC=C1.CC1(CC(C(=O)O)=CC=C1)C(=O)O DCNKXMWSUJCATR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000004646 arylidenes Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- KKHUSADXXDNRPW-UHFFFAOYSA-N malonic anhydride Chemical compound O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- SMBBZHGTZJNSRQ-UHFFFAOYSA-N n'-(6,6-dichlorohexyl)methanediimine Chemical compound ClC(Cl)CCCCCN=C=N SMBBZHGTZJNSRQ-UHFFFAOYSA-N 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2887—Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]
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- Y10T428/2852—Adhesive compositions
- Y10T428/2896—Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
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- Adhesives Or Adhesive Processes (AREA)
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- Adhesive Tapes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
A thermosetting resin composition for a fixing treatment of electronic parts, which is able to adhere in short time at low temperature, has a heat resistance, is lowly hygroscopic, and hardly produces package cracks, etc. The thermosetting resin composition comprises polycarbodiimide which is soluble in organic solvents and silicone-modified polyimide which is soluble in organic solvents.
Description
The present invention relates to a kind of novel hot setting resin composition.Compositions of thermosetting resin of the present invention is as the fixing tackiness agent of handling electricity and electronic unit such as semiconductor chip.
Paste binder and be known as the fixing tackiness agent of handling electricity and electronic unit such as semiconductor chip, substrate and lead with the product of adhesive coated on the thermotolerance material.Thermosetting resin such as Resins, epoxy, acrylic resin and rubber-phenol resins have been used as this tackiness agent, and still, hot setting was handled when they need be grown by heating, and the serviceability of tackiness agent is relatively poor.In addition, also there are some other problems, when being heating and curing, can produce a large amount of plumbous volatile constituents that contains; Because its high-hygroscopicity through the adverse current welding, can produce cracking.Therefore, for fixing processing electricity and electronic unit, conventional tackiness agent can't say to have very high reliability, up to now, does not also have gratifying tackiness agent available.
In addition, the hot melt build film adhesive of use thermoplastic polyimide resin can be bonding in short-term by heating, need not additional solidification process after bonding.But, because of its second-order transition temperature height, need very high temperature for processing, thus probably adherend is caused pyrolytic damage.
On the other hand, when the tackiness agent that uses low Tg when giving the machining at low temperature performance, the problem of existence is that thermotolerance is relatively poor, and reliability greatly reduces.For example, the second-order transition temperature of polycarbodiimide is low, and it has good binding property and low-temperature processability, but its reliability is very poor, when the atmosphere that is placed on high temperature and high pressure in the time of following tens hours, can lose bond strength.In order to solve this problem of polycarbodiimide, can in its molecule, introduce siloxane backbone to improve its reliability.Yet most commercial is a fatty substances as the silicone-modified vulcabond of raw material monomer, thereby the problem of existence is exactly that they have activity when producing polycarbodiimide.And then silicone-modified aromatic diisocyanate is difficult to synthetic usually, and the product instability causes and can not actually use.Thereby, still wish by making polycarbodiimide and other polymkeric substance blending but not use polycarbodiimide to improve wet fastness separately.
Nadiimide blending by polycarbodiimide and diaryl are replaced can improve physicals.JP-A-7-286140 (this paper term " jp-A " is meant " not examining Japanese patent application ") discloses the thermosetting coating with excellent heat resistance, and it comprises said n adiimide.JP-A-7-258353 discloses a kind of resin combination, comprises the blend of said n adiimide and bismaleimide.JP-A-7-330872 discloses resin combination, and it comprises the blend of said n adiimide and Resins, epoxy.But when it was used as tackiness agent, bond strength and flexibility did not reach gratifying degree.
And then JP-A-62-1714,5-239427 and 5-320611 all disclose the adhesive resin composition that obtains by blending Resins, epoxy and polycarbodiimide resin.But the package stability of Resins, epoxy and water absorbability still have problems, and still fail to reach satisfied result.
On the other hand, though polyimide has good thermotolerance usually, they can not be dissolved in the organic solvent under many situations, thus can not with the polycarbodiimide blending.Usually, they often use with the form of polyamic acid, and polyamic acid is the precursor of polyimide, thereby improves the miscibility of polyimide and other polymkeric substance.Yet, when desiring to be polycarbodiimide with its blended polymkeric substance, the problem of existence be its can with the carboxyl reaction in the polyamic acid, make the stability of solution become bad greatly.
Through further investigation, having obtained a kind of can need be cohesible resin combination only at low temperatures very short time, its good heat resistance, and water absorbability is low, and seldom can produce the packing cracking.Found that and preferably to mix soluble polyimide and solubility polycarbodiimide resin.In view of the above, finished the present invention.
Thereby, having an object of the present invention is to provide a kind of resin combination, it comprises polycarbodiimide that dissolves in organic solvent and the polyimide that dissolves in organic solvent.
Another object of the present invention has provided a kind of adhesive sheet, and it comprises compositions of thermosetting resin separately, perhaps comprises a kind of carrier and provided thereon and is the compositions of thermosetting resin of sheet form.
The polycarbodiimide that is preferred for resin combination of the present invention has the repeating unit of following formula (1) expression:
Wherein, X represents hydrogen atom or fluorine atom, and I is the integer of 2-400.
Preferred polyimide comprises the repeating unit by following general formula (2) and (3) expression:
R wherein
SiBe the siloxane diamine residue; R
10Be the diamines residue; R
20Be acid dianhydride (aciddianhydride) residue; (m+n) be the integer of 6-200, also comprise diamines and/or contain the acid dianhydride structural unit of the group of following formula (4) expression:
Wherein, X is hydrogen atom or fluorine atom.(1) polycarbodiimide
First kind of component of resin combination of the present invention is the polycarbodiimide that dissolves in organic solvent.The preferred embodiment of polycarbodiimide is represented by following formula (1):
Wherein, X is hydrogen atom or fluorine atom; I is the integer of 2-400, preferred 7-200.
If I is less than 2, its reliability is relatively poor behind injection moulding film forming or analogue, and if I greater than 400, then the package stability of solution is poor, and solution can not be durable when reality is used.
In the presence of phosphorus type catalyzer, can make polycarbodiimide by the corresponding vulcabond of ordinary method polymerization.
Vulcabond also can adopt the ordinary method preparation.For example, accordingly such as 2, two [4-(the 4-amino-benzene oxygen) phenyl] propane (BAPP) or 2 of 2-, the diamines of two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (BAPF) of 2-is used as precursor, and these diamines can carry out isocyanation esterification with phosgene, diphenyl carbonate, trimethylammonium chlorosilane etc.In addition, corresponding di-carboxylic acid also can be used as the precursor of this isocyanic ester, then with Ku Ertisi degraded carrying out isocyanation esterification.
Producing in the polycarbodiimide process by the polymerization vulcabond, can be used alone vulcabond, perhaps this vulcabond and other vulcabond carry out copolymerization, and its consumption is 60moi% or still less, in this scope, it is bad that performance can not become.The vulcabond that can be used for copolymerization is an aromatic diisocyanate, the example is 1,3-or 1, two (the 4-isocyanato-phenoxy group) benzene of 4-, 2,4-or 2, the 6-inferior cresyl vulcabond, 4,4 '-two isocyanato-s-2,2 '-dimethyl or two (trifluoromethyl) biphenyl, two isocyanato-ditans, 1-p-methoxy-phenyl-2, the 4-vulcabond, 3,3 '-dimethoxy-4 ', 4 '-diphenylmethanediisocyanate, 4,4 '-diphenyl ether vulcabond, 3,3 '-dimethyl-4,4 ' diphenyl ether vulcabond and adjacent inferior cresyl vulcabond, but the present invention is to itself and indefinite.
The catalyzer that is used for the polymerization vulcabond can be conventional phosphorus catalyst.For example, can adopt in the phosphorene oxide compound any, for example, 1-benzene pour-2-phosphorene-1-oxide compound, 3-methyl-2-phosphorene-1-oxide compound, 1-ethyl-2-phosphorene-1-oxide compound, 3-methyl isophthalic acid-benzene pour-2-phosphorene-1-oxide compound and its 3-phosphorene isomer.With the 1mol vulcabond, catalyst consumption is generally 0.1-20mol%, is preferably 0.3-10mol%, more preferably 0.5-5.0mol%.If catalyst consumption is too little, its meeting inactivation in reaction process, and reaction can stop.And if catalyst consumption is too big, then restive reaction.
Temperature of reaction in the polymerization process is generally 50-200 ℃, and preferred-10-150 ℃, more preferably 20-120 ℃.According to vulcabond that is adopted and solvent, can suitably change temperature of reaction.If temperature of reaction is too low, reaction may not carried out.On the other hand, if temperature is too high or heat-up time is oversize, undesirable side reaction may take place, perhaps product can decompose.Therefore, the proposal reactions temperature little by little begins to heat up from low temperature by following response such as IR.
Used reaction solvent can be any solvent, as long as it can dissolve or the suspension vulcabond.The example of solvent is ether compound tetrahydrofuran (THF), diox or diethyl ether; Halohydrocarbon such as methylene dichloride, chloroform, ethylene dichloride or tetrachloroethane; Ketone such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or cyclohexanone; Aromatic hydrocarbons such as toluene, dimethylbenzene or benzene.These solvents can be used singly or in combination.If desired with necessity, in reaction process, can partly or entirely replace solvent, thereby change temperature of reaction.
The concentration of the vulcabond in the reaction mixture is 1-50wt%, preferred 5-40wt%, more preferably 10-30wt%.If concentration is too low, the reaction times can be longer, and this is unpractical.On the other hand, if concentration is too high, then may produce side reaction, perhaps reaction process can not be controlled, and this is not a kind of optimal way.(II) polyimide
Second kind of component in the resin combination of the present invention is the polyimide that dissolves in organic solvent.Preferred polyimide comprises the isopropylidene structure of hexafluoro isopropylidene structure or formula (4) expression, and is included in R in the formula (2)
SiThe siloxane structure unit of expression.Therefore, preferred polyimide is
(a) comprise imide by the repeating unit of following formula (2) and (3) expression:
R wherein
SiExpression siloxane diamine residue; R
10Expression diamines residue; R
20Expression acid dianhydride residue; (m+n) be the integer of 6-200;
(b) content of silicone-modified diamines structural unit is 10-100% in the diamines structural unit; With
(c) comprise by the ratio of the total amount (b) of the hexafluoro isopropylidene structure of following formula (4) expression or isopropylidene structure diamines and anhydride structural unit with the total amount (a) of acid dianhydride structural unit except that silicone-modified diamines structural unit and diamines structural unit, be b/a, be 10-100%
Wherein X represents hydrogen atom or fluorine atom.
Polyimide with this structure can be miscible with polycarbodiimide well, makes good bonding between the resin combination of formation and substrate.
In addition, if (m+n) value is lower than above-mentioned scope, then the reliability of resin can reduce, and if should value greater than above-mentioned scope, then compatibility can variation.
Monomer is as described below, introduces following (i) and (ii) it is necessary
(i) a kind of silicone-modified diamines that has by the siloxane structure of formula (2) expression; With
(ii) by the structural unit isopropylidene or the hexafluoro isopropylidene structure of formula (4) expression, its basic structure in soluble polyimide chain of the present invention.(i) silicone-modified diamines
Be used for introducing siloxane structure (R to polyimide
Si: the silicone-modified diamines siloxane diamine residue) is preferably the diamino polysiloxane by following formula (5) expression:
R wherein
1And R
2Be respectively bivalent hydrocarbon radical; R
3-R
6Be respectively the alkyl of 1-6 carbon atom, preferable methyl or ethyl; K is the integer of 1-20, preferred 1-6.R
1And R
2Be preferably the alkylidene group that comprises methene chain, the arylidene of aromatics divalent group, R
1And R
2More preferably identical group.The specific examples of diamino polysiloxane compound is following diamines
These silicone-modified diamines can use separately or use with two or more blended forms.The content of silicone-modified diamines structural unit is 10-100mol% in the diamines structural unit, preferred 20-80mol%.If the content of silicone-modified diamines structural unit is less than above-mentioned value, then compatibility and fusible improvement are not enough, and if greater than above-mentioned value, be non-remunerative from considering economically then.The (ii) monomer of drawing-in system (4) structural unit
Explained later is introduced by the isopropylidene structural unit of following formula (4) expression or the monomer of hexafluoro isopropylidene structural unit.
The monomer example of introducing these structural units is following diamines except that silicone-modified diamines, and the carboxylic diacid acid anhydride.
(ii-a) (it introduces diamines residue, i.e. R to the diamines except that silicone-modified diamines
10).
The example of this diamines is 2, two [4-(3-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa and 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-.
(ii-b) (it introduces acid dianhydride residue, i.e. R to the carboxylic diacid acid anhydride
20)
The example of tetracarboxylic acid dicarboxylic anhydride is 2, two (2,3-or 3,4-dicarboxyl phenyl) the propane dicarboxylic anhydrides and 2 of 2-, two (2,3-or 3,4-or 3,4-dicarboxyl phenyl) the HFC-236fa dicarboxylic anhydrides of 2-.
Carboxylic diacid acid anhydride structural unit is 10-100mol% with the ratio of the total amount (a) of the total amount (b) of the diamines structural unit with structural unit of being represented by formula (4) and acid dianhydride structural unit except that silicone-modified diamines structural unit and diamines structural unit, preferred 30-100mol%.If (b/a) value is less than 10%, then polycarbodiimide and its can not mix.(iii) (it introduces the R except that last to other diamine components
10)
Other diamine components of using with above-mentioned diamine components can be any aromatic diamine.The example of aromatic diamine be to or m-phenylenediamine, 4,4 '-, 3,4 ', 2,4 ' or 3,3-diamino-diphenyl ether, 4,4 '-, 3,4 ' or 3, the 3-diamino diphenyl sulfone, 4,4 '-, 3,4 ' or 3,3 '-diamino-diphenyl sulfide, 4,4 '-, 3,4 ' or 3,3 '-diamino benzophenone, 4,4 '-, 3,4 ' or 3,3 '-diamino-diphenyl propane, 4,4 '-, 3,4 ' or 3,3-diamino-diphenyl HFC-236fa, two [4-(3-or 4-amino-benzene oxygen) phenyl] methane, 1, two (3-amino-benzene oxygen) benzene of 3-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, two [4-(3-or 4-amino-benzene oxygen) phenyl] sulfone and two [4-(3-or 4-amino-benzene oxygen) phenyl] ether.They can use separately or use with two or more form of mixtures.Formula is other acid anhydrides (R of its introducing except that last (iv)
20)
Other acid anhydrides is the tetracarboxylic acid dicarboxylic anhydride except that the tetracarboxylic acid dicarboxylic anhydride of the structural unit with above-mentioned formula (4) expression.This example that can be used for the carboxylic diacid acid anhydride of above-mentioned diamine components reaction is 1,2,4,5-pyromellitic acid dicarboxylic anhydride, 2,2 ', 3,3 '-or 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, oxygen connection phthalic acid dicarboxylic anhydride, 2,2 ', 3,3-benzophenone tetracarboxylic acid dicarboxylic anhydride, or 3,3 ', 4,4-benzophenone tetracarboxylic acid dicarboxylic anhydride, 2, two (3,4-dicarboxyl phenyl) the sulfone dicarboxylic anhydrides of 2-, two (2,3-or 3,4-dicarboxyl phenyl) the methane dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, two (2,3-or 3,4-dicarboxyl phenyl) methylene fluoride dicarboxylic anhydride, 1, two (3,4-dicarboxyl phenyl)-1,1 of 3-, 3,3-tetramethyl disiloxane and its derivative.They can use separately or use with two or more form of mixtures.[production method of polyimide]
The polyimide that dissolves in organic solvent can be synthetic according to ordinary method.That is, above-mentioned diamines reacts in a kind of solvent with the tetracarboxylic acid dicarboxylic anhydride of equimolar amount almost, and preparation polyamic acid (precursor of polyimide) makes the polyamic acid imidization to obtain polyimide by heating or chemical means.
For example, chemistry imidization method is, will add in the polyamic acid such as the dewatering agent of dichloro hexyl carbodiimide, trifluoroacetic anhydride, thionyl chloride or phosphorus trichloride, makes the mixture of formation under agitation carry out ring-closure reaction, work is if desired cooled off simultaneously.The reaction mixture that forms is filtered, and the filtrate that obtains is poured in precipitation agent such as the 2-propyl alcohol to be settled out reaction product.Leach precipitation, washing, drying obtains required polyimide powder.
On the other hand, can under 150 ℃ or higher temperature, carry out the imidization process by the solvent by the heating polyamic acid, to finish the dehydration closed-loop reaction.In order effectively water byproduct to be removed, can add solvent such as dimethylbenzene or toluene simultaneously from system.In addition, use organic bases such as triethylamine, isoquinoline 99.9 or pyridine can promote the imidization rate.Polyimide by heating method imidization preparation can directly use, and also can precipitate in 2-propyl alcohol or methyl alcohol and forms powder and re-use by being dissolved in organic solvent more subsequently.
The organic solvent that can be used for above-mentioned polyreaction comprises N-first-2-Pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, 1,3-dimethyl-2-imidazolone, dimethyl sulfoxide (DMSO), dimethyl sulphide, dimethyl sulfone, pyridine, tetramethyl-urea, diglyme, triglyme, tetrahydrofuran (THF), diox and pimelinketone.They can be used singly or in combination.
With the work of necessity, soluble polyimide of the present invention can adopt Tetra hydro Phthalic anhydride or derivatives thereof or aniline or derivatives thereof to hold envelope if desired.(preparation of compositions)
The present invention comprise polycarbodiimide as the resin solvent of main ingredient can use in polycarbodiimide solution add and dissolving soluble polyimide powder or earlier with the soluble polyimide powder dissolution in organic solvent, the polycarbodiimide of the solution of the soluble polyimide that forms is mixed being prepared again.Used organic solvent can be any organic solvent that can dissolve soluble polyimide and polycarbodiimide.Particularly, can adopt the identical organic solvent that is used for above-mentioned polymerization process.
In the polycarbodiimide as major constituent of 100 weight parts, the amount of soluble polyimide is the 0.1-50 weight part in the resin combination of the present invention, preferred 1-30 weight part, more preferably 2-20 weight part.If the soluble polyimide amount very little, its internal performance can not show.On the other hand, if it is too big, the characteristic that will lose polycarbodiimide is as low Tg and agent of low hygroscopicity.In addition, also may be separated in the resin.
Heat-resistant resin composition of the present invention can mix with fine mineral filler, and its consumption would not damage the processibility and the thermotolerance of resin combination.In addition, if necessary, can add various additives such as defoamer, even paint or be used to make the smooth agent of surface smoothing.(adhesive sheet)
Comprise polycarbodiimide of the present invention and can make film according to ordinary method, thereby obtain adhesive sheet as the varnish of main ingredient.The thickness of this adhesive sheet is generally 1-2000um, but this thickness is not determinate, and it can suitably be selected according to adhesive applications.In addition, the shape of adhesive sheet and size also can suitably change according to adherend such as lead or semiconductor chip.
If necessary, as in order to give electroconductibility, improve thermal conduction and control elasticity, particularly realize snappiness, when forming adhesive sheet, can one or more inorganic powders of blending, comprise metal or alloy (as aluminium, copper, silver, gold, nickel, chromium, lead, tin, zinc, palladium and solder flux), pottery (as aluminum oxide, silicon-dioxide, magnesium oxide and silicon nitride), carbon etc.
The coating temperature of film is 20-300 ℃, preferred 50-250 ℃, and more preferably 70-200 ℃.If coating temperature is lower than 20 ℃, solvent also can be remaining in film, and if this value is higher than 300 ℃, then film may thermofixation.
And then, can on carrier, form film.In the preparation process of the adhesive sheet of constructing like this, varnish can be coated on the carrier, perhaps established rete can be depressed on the carrier by means such as compactings.
Tinsel, insulating film etc. can be used as carrier.The example of adoptable tinsel comprises aluminium, copper, silver, gold, nickel, indium, chromium, lead, tin, zinc, palladium etc.They can use separately or use with the alloy that comprises two or more metals.Insulating film can be any and has thermotolerance and chemical-resistant film.The example comprises polyimide, polyester, polyethylene terephthalate etc.
Tinsel and insulating film can use separately, perhaps with two or multiwalled laminate carrier form use, it has for example structure of tinsel/insulating film, prepares by lamination.The example of two-layer matrix is the two-layer matrix of copper/polyimide.
Adhesive sheet of the present invention has very strong binding property because of carrying out thermofixation by thermal treatment, simultaneously, obtains a kind of low moisture absorptivity solidifying product.Thermal treatment can be undertaken by suitable mode, as well heater, ultrasonic wave or ultraviolet ray.Thereby adhesive sheet of the present invention preferably can be used for various materials are carried out adhesion process, and the immobilization that is particularly preferred for electricity and electronic unit is handled, and promptly the semiconductor chip and the lead of need agent of low hygroscopicity is handled.
Adhesive sheet of the present invention has good water absorbability, high flexibility thereby is easy to be handled, can bonding well semiconductor element, and have good storing stability.
By coating resin combination varnish of the present invention on a side of tinsel, be dried again and the tinsel with binder layer that obtains is specially adapted to the production of multilayer line matrix etc.
Further specify compositions of thermosetting resin of the present invention by following embodiment and comparative example.
Measure the performance of the resin combination that forms by following method.Second-order transition temperature (Tg)
Adopt Seiko ssc/560M (Seiko Corp. production) that sample is heated to 400 ℃ from room temperature, temperature rising speed is 10 ℃/minute.Bonding:
Resinous varnish is spun on the siloxane sheet.The siloxane sheet of coating is placed in the pressure-cooking (TABAI PRESSURE COOKER TPC-411) of 120 ℃/100%RH.Estimate before and after the thermal treatment bondability that contacts between resin and siloxane sheet.Evaluation method is, from 100 1mm
2Grid on the grid number peeled off be defined as " n ", n/100 is used to estimate (crosscut test).Use ShimadzuAutograph AGS-100D to measure its bond strength with 180 ° of stripping strengths.
Synthetic embodiment 1 synthesis of polyimides 1:
In the separable flask of the 500ml that has condenser and agitator, add 2 of 21.72g (42mmol), two (aminopropyl) tetramethyl disiloxanes (APDS) of two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (BAPF) of 2-, 10.70g (42mmol) and the N-N-methyl-2-2-pyrrolidone N-(NMP) of 186sg.In room temperature and under stirring, to 2,2 pairs of (3,4-dicarboxyl phenyl) sulfone dicarboxylic anhydrides wherein pouring 30.02g (84mmol) into.The mixture that forms was at room temperature stirred 3 hours, and then stirred 4 hours down, to realize imidization by heating at 180 ℃.The varnish that obtains is heavy again in methyl alcohol, filters, and obtains a kind of powder.With this powder 150 ℃ dry 1 hour down, be dissolved in the varnish that makes a kind of 30wt% in the pimelinketone (below be referred to as " p11 ") again.
Synthetic embodiment 2 synthesis of polyimides 2:
According to synthetic embodiment 1 identical method prepare polyimide varnish (below be referred to as " p12 ",) just two [4-(3-amino-benzene oxygen) phenyl] sulfones (3-BAPS), 10.70g (42mm) two (aminopropyl) tetramethyl disiloxane (APDS) of 20.35g (42mmol) are used as diamine components, 37.3g (84mmol) 2, two (3,4-dicarboxyl phenyl) the HFC-236fa dicarboxylic anhydrides of 2-are as acid anhydrides.
Synthetic embodiment 3 synthetic polycarbodiimides: in the 101 separable flasks that have dropping funnel, condenser and agitator, add 2 of 800g (1.54mol), two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (BAPF) of 2-, the triethylamine of 312g (3.09mol) and 81 toluene.By heating BAPF is dissolved fully, again to the phenyl chloroformate that wherein drips 183g (3.09mol).The mixture cooling of formation is produced to suppress heat, stirred liquid to finish reaction.Add triethylamine (281g again; 2.78mol), at room temperature will place the trimethylammonium chlorosilane of the 302g (2.78mol) of dropping funnel to drop to wherein.After finishing dropping, add 3-methyl isophthalic acid-phenyl-2-phosphorene-1-oxide compound again, the mixture that forms was stirred 9 hours, simultaneously elevated temperature to 80 ℃ gradually as the 29.7g (0.154mol) of the catalyzer of carbodiimideization.After confirming that by IR reaction is finished, reaction mixture is cooled to room temperature, leach the salt of formation.The solvent of the varnish that forms is replaced with pimelinketone, obtains the solution of 20wt%.Below this varnish be referred to as " PCD ".
Embodiment 1
Above-mentioned p11 and PCD are mixed with varnish with solid ratio as shown in table 1 below.Each varnish product each other all can be compatible and can not be separated.The varnish that forms is spun on the siloxane sheet, and drying is 30 minutes under 90 ℃, again 250 ℃ of following thermal treatments 1 hour.By pressure-cooking method of testing (PCT) water tolerance is tested then.Table 1 shows the physicals and the bonding evaluation result (cross-section method) of each varnish.
Table 1
After clear coat composition bond properties varnish number (parts by weight) PCT handles
PCD PI1 Tg (℃) initial value (20 hours) 1 100 0 150 0/,100 10,0/1,002 100 2.5 155 0/,100 1,3/1,003 100 5 159 0/,100 0/100
Embodiment 2
Synthetic PI2 makes itself and PCD be mixed with varnish with ratio of mixture shown in the table 2 as polyimide among the synthetic embodiment 2.These varnish products each each other all can be compatible and can not be separated.Handle the various varnish products that form and it is estimated with the method identical with embodiment 1.Table 2 shows the physicals and the cross-section method test result of each varnish product.
Table 2
After clear coat composition bond properties varnish number (parts by weight) PCT handles
PCD PI2 Tg (℃) initial value (20 hours) 4 100 2.5 150 0/,100 2,0/1,005 100 5 153 0/,100 0/100
Embodiment 3
The varnish 3 of implementing 1 preparation is coated (35 μ m) on the copper sheet, and drying is 20 minutes under 200 ℃, makes a kind of adhesive sheet (thickness: 20 μ m).It is sticked on one 42 alloy slice, and they are at 50kg/cm
2Pressure and 350 ℃ of following 2 seconds adherent of compacting.Measuring bond strength, is 1,400g/cm.Transferring the postpone bond strength in the constant temperature and constant humidity condition of 80 ℃/90%RH is 800g/cm.
Embodiment 4
With the test of the mode identical to carrying out according to the bond strength of the varnish 5 of embodiment 2 preparations with embodiment 3, be 1 under conventional state, 200/cm.Bond strength is 750g/cm after rotating 168 hours under the constant temperature and constant humidity condition of 80 ℃/90%RH.
Comparative example 1
In the mode identical with embodiment 3 bond strength according to the varnish 1 of embodiment 1 preparation being tested, is 1 under conventional state, 400g/cm.After placing 168 hours under the constant temperature and constant humidity condition of 80 ℃/90%RH, occur separating.
Comparative example 2
Prepare polyimide in the mode identical with synthetic embodiment 1, just adopt 3,3-diamino diphenyl sulfone, two (aminopropyl) tetramethyl disiloxane (APDS) and oxygen connection phthalic acid dicarboxylic anhydride (ODPA) are as monomer.The polyimide that forms can not be miscible with PCD when mixing with PCD, and they can be separated into independently phase.
Comparative example 3
PCD is mixed with polyimide varnish (being produced by General Elcetric).But owing to lack compatibility between them, they are separated into independently phase.
The second-order transition temperature of resin combination of the present invention is 200 ℃ or lower, thereby its machining at low temperature performance improves.And then it can be bonded on adherend such as the semiconductor element well, and because of agent of low hygroscopicity has excellent in storage stability, thereby prolonged preservation at room temperature.
Abovely the present invention is had been described in detail, but those skilled in the art can find out significantly that all various variations all do not deviate from spirit of the present invention and protection domain in conjunction with specific embodiment.
Claims (5)
1, a kind of compositions of thermosetting resin comprises polycarbodiimide that dissolves in organic solvent and the polyimide that dissolves in organic solvent.
2, according to the compositions of thermosetting resin of claim 1, wherein said polycarbodiimide is represented by following formula (1):
Wherein X is hydrogen atom or fluorine atom, and I is the integer of 2-400.
3, according to the compositions of thermosetting resin of claim 1, wherein
(i) said polyimide has the repeating unit by following general formula (2) and (3) expression:
R wherein
SiBe the siloxane diamine residue; R
10Be the diamines residue; R
20Be the acid dianhydride residue; (m+n) be the integer of 6-200;
(ii) the structural unit amount of silicone-modified diamines is 10-100% in the diamines structural unit; With
(iii) comprise by the ratio of the total amount (b) of the diamines structural unit of the group of following formula (4) expression and acid dianhydride structural unit with the total amount (a) of acid dianhydride structural unit except that silicone-modified diamines structural unit and diamines structural unit, be b/a, be 10-100%.
4, a kind of film that comprises claim 1,2 or 3 resin combination.
5, a kind of adhesive plate, it comprises carrier and binder layer, and this binder layer is included in the claim 1 that forms at least one side of this carrier, 2 or 3 resin combination.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP102766/97 | 1997-04-04 | ||
| JP9102766A JPH10279799A (en) | 1997-04-04 | 1997-04-04 | Thermosetting resin composition |
| JP102766/1997 | 1997-04-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1197819A true CN1197819A (en) | 1998-11-04 |
| CN1113937C CN1113937C (en) | 2003-07-09 |
Family
ID=14336311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98108759A Expired - Fee Related CN1113937C (en) | 1997-04-04 | 1998-04-04 | Thermosetting resin composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6068932A (en) |
| EP (1) | EP0869151B1 (en) |
| JP (1) | JPH10279799A (en) |
| KR (1) | KR19980081051A (en) |
| CN (1) | CN1113937C (en) |
| DE (1) | DE69821664T2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906813A (en) * | 2016-06-05 | 2016-08-31 | 吉林大学 | Method for preparing regular block copolymerization polyimide siloxane single-layer film |
| CN108864932A (en) * | 2017-05-11 | 2018-11-23 | 信越化学工业株式会社 | Silicone-modified polyimides resin combination |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4435919B2 (en) * | 2000-01-11 | 2010-03-24 | 日東電工株式会社 | Adhesive composition |
| JP2001207055A (en) * | 2000-01-25 | 2001-07-31 | Nitto Denko Corp | Carbodiimide resin composition |
| JP4522604B2 (en) * | 2001-03-19 | 2010-08-11 | 日東電工株式会社 | Anisotropic conductive film |
| US7129318B2 (en) * | 2003-09-02 | 2006-10-31 | I.S.T. (Ma) Corporation | RTM and RI processable polyimide resins |
| KR100687926B1 (en) | 2005-06-13 | 2007-02-27 | 삼성전자주식회사 | Liquid crystal display |
| WO2019073891A1 (en) * | 2017-10-10 | 2019-04-18 | 三井金属鉱業株式会社 | Resin composition for printed wiring board, copper foil with resin, copper-clad laminate board, and printed wiring board |
| JP6844570B2 (en) * | 2018-03-29 | 2021-03-17 | 信越化学工業株式会社 | Silicone rubber-silicone modified polyimide resin laminate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2615343C2 (en) * | 1976-04-08 | 1984-09-27 | Bayer Ag, 5090 Leverkusen | Polymer combinations |
| JPS621714A (en) * | 1985-06-28 | 1987-01-07 | Nisshinbo Ind Inc | Thermosetting resin and production thereof |
| JP3713283B2 (en) * | 1992-02-28 | 2005-11-09 | 日清紡績株式会社 | Heat resistant adhesive composition |
| JPH05320611A (en) * | 1992-05-18 | 1993-12-03 | Nisshinbo Ind Inc | Filmy adhesive composition |
| EP0708795A4 (en) * | 1993-07-15 | 1996-08-07 | Univ Akron | Heat-resistant polyimide blends and laminates |
| US5576398A (en) * | 1995-07-07 | 1996-11-19 | Japan Synthetic Rubber Co., Ltd. | Thermosetting resin composition |
| EP0810244B1 (en) * | 1996-05-29 | 2003-04-09 | Nitto Denko Corporation | Aromatic polycarbodiimide and sheet using it |
| US5830949A (en) * | 1996-09-26 | 1998-11-03 | Nitto Denko Corporation | Adhesive resin composition and adhesive sheet |
-
1997
- 1997-04-04 JP JP9102766A patent/JPH10279799A/en active Pending
-
1998
- 1998-04-01 DE DE69821664T patent/DE69821664T2/en not_active Expired - Fee Related
- 1998-04-01 EP EP98105988A patent/EP0869151B1/en not_active Expired - Lifetime
- 1998-04-02 US US09/053,782 patent/US6068932A/en not_active Expired - Fee Related
- 1998-04-03 KR KR1019980011746A patent/KR19980081051A/en not_active Application Discontinuation
- 1998-04-04 CN CN98108759A patent/CN1113937C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906813A (en) * | 2016-06-05 | 2016-08-31 | 吉林大学 | Method for preparing regular block copolymerization polyimide siloxane single-layer film |
| CN108864932A (en) * | 2017-05-11 | 2018-11-23 | 信越化学工业株式会社 | Silicone-modified polyimides resin combination |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19980081051A (en) | 1998-11-25 |
| DE69821664D1 (en) | 2004-03-25 |
| EP0869151A2 (en) | 1998-10-07 |
| CN1113937C (en) | 2003-07-09 |
| JPH10279799A (en) | 1998-10-20 |
| EP0869151A3 (en) | 1998-11-18 |
| DE69821664T2 (en) | 2004-07-08 |
| US6068932A (en) | 2000-05-30 |
| EP0869151B1 (en) | 2004-02-18 |
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